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DR. BABASAHEB AMBEDKAR TECHNOLOGICAL UNIVERSITY, LONERE P. S. G. V. P. MANDAL’S D. N. PATEL COLLEGE OF ENGINEERING SHAHADA, DIST- NANDURBAR “MICROBIAL FUEL CELLS” SUBMITTED BY Mrs. KANCHAN HIMMAT PAWAR PRN.NO. 1951641293021 UNDER THE GUIDANCE OF PROF. PANKAJ. R. PATIL DEPARTMENT OF ELECTRICAL ENGINEERING YEAR 2022-23 P. S.G. V. P. MANDAL’S D. N. PATEL COLLEGE OF ENGINEERING, SHAHADA, DIST. NANDURBAR "CERTIFICATE This is to certify that Mrs. KANCHAN HIMMAT PAWAR PRN.NO. 1951641293021 Haye been satisfactorily completed Seminar entitled on “MICROBIAL FUEL CELLS” Asa part of syllabus of DR. BABASAHEB AMBEDKAR TECHNOLOGICAL UNIVERSITY, LONERE For the partial fulfillment of Bachelor of Technology in ELECTRICAL ENGINEERING. In the Academic Year 2022-23 SEMINAR GUIDE HOD. PROF. PANKAJ. R. PATIL PROF, Smt. K.A, PATEL PRINCIPAL PROF. Dr. N. J. PATIL CKNOWLEDGMENT The acknowledgment is just like a drop in the ocean of the deep sense of gratitude within my heat for people who help me out of most embarrassing part of my life when I am standing at most difficult step towards my dream of life. 1 fill great pleasure in submitting the Seminar report on “MICROBIAL FUEL, CELLS” I wish to express true of sense gratitude towards my seminar guide Prof. PANKAJ R. PATIL who guide at very discrete step in studying of this seminar and contributed his valuable guidance and help to solve problems that arises. I would also like to thanks our H.O.D. Prof. St K. A. PATEL & other staff ‘members who support me at various stages white compiling this report. I would also like to thanks our friends, who really helpful to me for my seminar I work & for programming of our seminar 1 am grateful to Mighty God inspiring my parents and beloved ones whose loving and caring supports contributed a major share in completion of my seminar report. I owe my all success to them. Mrs. KANCHAN HIMMAT PAWAR PRN. 1951641293021 ROLL NO. 19 Sr.No Index Particulars Abstract INTRODUCTION LITERATURE SURVEY 2.1 History CONSTRUCTION AND SAFETY 3.1 Wastewater Treatment 3.2 Sediment MFC (SMFC) 33 Designs 344 Materials And Substrate: PERFORMANCE AND SCALING UP. MATERIALS AND METHODS 5.1 Experimental Set Up 5.2 Confocal Microscopy 5.3 Discussion ELECTRICITY GENERATION ADVANTAGES: CONCLUSION REFERENCES Page No. Figure no, Figure 3.1 Figure 3.2 Figure 32 Figure 5.1 Figure 5.2 CONTENTS List of Figures Title Sediment MFC 29). ‘Types of MFCS Used In Studies MECS Used For Continuous Operation ‘Schematic Diagram of MFCS Used In Study Experimental sot up. Page no. ABSTRACT ‘Microbial fuel cells (MFCs) are devices that exploit microbial catabolic activities to generate electricity from a variety of materials, including complex organic waste and renewable biomass, These sources provide MFCs with a great advantage over chemical fuel cells that can utilize only purified reactive fuels (e.g., hydrogen). A developing primary application of MFCs is its use in wastewater treatment coupled with electricity generation, although further technical developments are necessary for its practical use. ‘The aim of this study was to test_a novel MPC design for wastewater treatment and simultaneous electricity production. Two identical MFCs of the design were used with high concentration substrate synthetic dairy wastewater with 4g of COD (chemical oxygen demand) per liter. The MFCs were run continuously at sub-ambient temperatures (150C) for 35 days from the 19th of January-22nd of February. The hypothesis of the design was to bring MFC s closer to large scale industrialization. As such the materials and mechanics of the design were conceived with the consideration of the needs of large scale wastewater treatment plants. Many tests were carried out to assess the condition for the bacteria within the two MFCs such as VFA, SMA. as well as the continuous recording of voltage and COD removal efficiency. SEM and confocal microscopy was also carried out to descrihe the bacteria being used. Published works and recent advances in MFC technologies that can become fundamentals for future practical MFC developments are reviewed and combined with the results of this experiment for evaluation and discussion, ‘The MBC design proved successful in that it achieved 60% removal efficiency, the predicted target whilst producing relatively high values of electricity compared to other MECs in the literature with the max power per volume value for both MFCs 84W m-3. The columbic efficiency for the two MFCs however was very low at only 2% due to the high concentration of COD in the substrate. This means only 2% of the wastewater treated was converted into energy. Chapter 1 INTRODUCTION As of 31/10/2011, there are over 7 billion people on the planet .Exploitation of the energy stored in fossil fuels has supported global industrialization and economic growth during the past one hundred and fifty years but it is obvious that this practice cannot be sustained. Oil will not actually run out for at least another 100 years or more but demand for oil is expected to exceed production capabilities from known and anticipated oil reserves within the 2015 to 2025 time frame. The use of carbon fuels is increasing the concentration of carbon dioxide in the atmosphere. Without substantial changes to our energy production methods, we will greatly exceed any historic level of CO2 concentrations in the atmosphere, Global mean temperatures have already risen to above pre-historic levels resulting in melting of glaciers and rising sea levels Whether you believe there is a link between the two or not, to believe that rapid production of a particular gas (CO2) and release of it into the atmosphere will not have some, effect on our atmosphere, global climate and hence biosphere is idiotic. The earth's collective biodiversity is experiencing its sixth major extinction event since multicellular life first evolved. Our population is increasing, our climate is changing rapidly and we are losing our main energy sources. | understand that “nothing endures but change”, however if change continues along this trend, we, most definitely will not endure. It sounds bad, but remembers ‘our one great virtue as humans, at least in theory, we have a choice. One choice we can make is to meet, head on, our greatest environmental challenge; to simultaneously solve energy production and reduce CO2 emissions. There is no silver bullet per se; it will most likely involve many ideas and methods of sustainable energy production, cone of which may be the development and use of microbial fuel cell technologies. Chapter 2 LITERATURE REVIEW ‘The purpose of this literary review is to organize relevant information and apply the principles of a feasibility study to MFC technology. MFCs (Microbial Fuel Cells) Electricity is our main source of power and is nothing more than a flow of electrons. A voltaic cell uses a spontancous oxidation coupled to reduction reaction to generate electricity. The cell is divided into two compartments where the oxidation (loss of electrons) and reduction (gaining of electrons) occur. Each compartment has an electrode where the reaction occurs. The electrode where oxidation occurs is called the anode (Negative -) and the electrode where reduction occurs is called the cathode (Positive +). Attracted by the positive cathode the negative electrons (opposites attract) flow from the anode along an external circuit where they must get through a resistor forcing them to carry out electrical work (heat, light etc. Microbial fuel cells works similarly to a voltaic cell, except they use the catalytic reaction of microorganisms such as bacteria to convert virtually any organic material into electricity. Some common substrates utilized by MFCs include glucose, acetate and wastewater. In an MFC, microorganisms degrade (oxidize: take electrons from) organic ‘matter, producing electrons that travel through a series of respiratory enzymes in the cell resulting in energy for the cell in the form Adenosine tri phosphate (ATP). The electrons are then released to a terminal electron acceptor (TEA) which accepts the electrons and becomes reduced (loses electrons)(3,5). Many TEAs such as oxygen, nitrate, sulphate, and others readily diffuse into the cell where they accept clectrons forming products that can then diffuse out of the cell However we now know that some bacteria can transfer electrons exogenously (outside of the cell) to a TEA such as a metal oxide like iron oxide. It is these bacteria that can exogenously transfer electrons, called exo electro gens that can be used in an MEC. The bacteria grow on the anode and oxidize organic matter, releasing electrons to the anode, and protons to the solution. The two electrodes are connected by a wire containing a load (1. the device being powered). The protons (H+) or other ions, filter through the membrane ensuring, electro neutrality. Protons may combine with the electrons transferred via the wire and oxygen, present in the water, forming water at the cathode, Thus by feeding the bacteria organic matter we get electrons and water. 2.1 HISTORY OF MICROBIAL FUEL CELLS Microbial fuel cells are the newest approach for generating electricity-bioelectricity generation from biomass using bacteria, Their history albeit brief, (only becoming of real interest in the early 1990°s), is an interesting one. The first MFC concept was demonstrated by MC Potter in 1910. Using platinum electrodes electricity was produced from living. cultures of Escherichia coli and Saccharomyces. In the 1980's it was discovered that current density and power output could be greatly enhanced by the addition of electron transfer mediators, or electron shuttles which can carry electrons from inside the cell to exogenous electrodes, the ‘middlemen’ in other words(3.7). Only anodo philes (exo electro gens) can directly transfer electrons directly to the anode. This is because the outer layers of the majority of microbial species are composed of non- conductive lipid membrane, peptidoglycans and lip polysaccharides that hinder the direct electron transfer to the anode, The problem with synthetic mediators in relation to MFCs is that they are unstable and toxic to most bacteria. A breakthrough was made however in 1999 when microbes were found to transfer electrons directly to the anode (our exo electro gens) The growth of the bacteria is supported by the very power production process we utilize (electron transfer) resulting in long term, stable power production Shewanella putrefactions, Geobacteraceae sulfur reduces, Geobacter metallireducens and Rhodoferax ferrite ducens are all bio electro chemically active species and can form a bio film on the anode surface and transfer electrons directly by conductance through their cell membrane. Here the anode acts as the final electron acceptor in the dissimulator respiratory chain of the microbes in the bio film. Bio films also form on the cathode surface and may also play an important role in electron transfer between the microbes. ‘They can also serve as electron donors for Thio bacillus faro oxidans suspended in a catholyte for an MFC system that contains microbes in both its anodic and catholic chambers. G. metallireducens and G. Sulfurreducens or other seawater-induced bio films may all act as final electron acceptors by grabbing the electrons from cathode as electron donors. Since the cost of a mediator is eliminated, mediator-less MFC are advantageous in wastewater treatment and power generation Modern MFCs can therefore be considered to have only emerged in 1999 with the finding of electricity gencration without the need for exogenous mediators. Chapter 3 SYSTEM DEVELOPMENT 3.1 WASTEWATER TREATMENT Probably the most important application of MFCs will be in wastewater treatment. Wastewater contains energy, in the form of biodegradable organic matter, that we expend energy to remove rather than trying to recover it. At a conventional wastewater treatment plant in Toronto, Canada, it was estimated that there was 9.3 times the energy in the ‘wastewater, than was used to treat it. MECs have been considered for treating waste water as early as 1991. Municipal wastewater contains a multitude of organic compounds that can fuel MFCs. Furthermore, organic molecules such as acetate, propionate, and butyrate can be thoroughly broken down, to CO2 and H20. MFCs using certain microbes have a special ability to remove sulfides as required in wastewater treatment (22). MBCs can enhance the growth of bio electrochemically active microbes during wastewater treatment thus they have good operational stabilities. Up to 80% of the COD can be removed in some cases and a Columbic efficiency as high as 80% has been recorded, Although the energy that could be captured from wastewater is not enough to power a city, it is large enough to someday power a treatment plant. With advances, capturing this power could achieve energy sustainability for the water infrastructure. There are four main advantages to using an MFC instead of one of the present conventional bioreactors such as the Activated Sludge (AS) process or the Trickling Filter (TF) process used for wastewater treatment. 1. Production of a useful product in the form of electricity. The current generated is dependent on the wastewater strength and as mentioned before Columbic efficiency. 2. Lack of a need for aeration. Aeration in AS can consume 50% of the electricity used at a treatment plant and is costly in many other conventional treatment processes. No aeration however is needed for an air cathode MFC and very little or none is needed for most other designs too, 3. Reduced solids production, The MFC is an anaerobic process, and thus bacterial biomass production will be reduced compared to that of an aerobic system such as TF or AS. Solids treatment is expensive, and using an MFC may substantially reduce solids production, 4, Potential for odour control. High surface areas needed in TFs exposed to air, and the flow of large amounts of air through the aeration basin in an AS process greatly increases the potential for odour generation to a surrounding community. MFCs require neither and should theoretically produce fewer o dours. However this area is, the least well studied aspect of MFC treatment performance. As such it is great potential for MPCs in wastewater treatment. clear there 3.2 SEDIMENT MFC (SMFC) There is even enough electricity to be generated from the bacterial decomposition of organic matter in marine sediments to power remote monitoring devices, by placing the anode electrode in the sediment and the cathode in the overlying water. The high salinity of the seawater provides good ion conductivity hetween the electrodes and the organic matter needed by the bacteria to produce electricity is already in the sediments, although relatively little electricity is produced, SMFCs are still probably going to he hugely important to the scientific community as, they are able to proce energy in remote and relatively inaccessible areas such asthe seabed = 5 =a Rete Hp 20, Copyrapi 2005 er Phe Cro Nature Reviaws|iicrblelogy Figure 3.1 Sediment MFC (29). SMECs can be used as a power source for devices placed on the seafloor, but could also serve as a type of “refueling station” for small autonomous devices that are operated in the underwater environment. (3)SMFCs are probably the closest MFCs to practical application, also known as a Benthic Unattended Generator or BUG for short 3.3 DESIGNS Since the main disadvantage of MFCs as a power source is their low power producing capability, it is important we identify the materials and designs that maximize power generation and coulombic efficiency. However it is also necessary to minimize cost and discard designs that are not inherently scalable if there is to be a practical future for MFCs. MFC designs can be classified into two types (1) Research type MFCs: These types are easy to construct and are used for short experiments. They are suited to inyestigate specific microbial processes or new materials. Due to their periodical batch operation, they are not appropriate for long term operation. In most cases, the electrochemical design is not optimized and does not allow high maximum power generation. Figure: 3. 2: Types of MFCS Used In Studies (A) Easily construeted system containing a salt bridge (shown by arrow); (B and C) four batch-type MFCs; (D) photo heterotrophic type MF (E) Single chambered, air cathode system; (F) two chamber H-type system. (2) Continuous MFCs: For long term MEC operation, MFCs are fed continuously with several substrates (e.g. glucose, acetate, sucrose, waste water) and continuously generate electricity. 6 These types can be used to investigate the evolution of the microbial community and electrochemical characteristics. The electrochemical parameters are optimized to generate high ‘maximum power outputs. }: MFCS Used For Continuous Operation (A and B) up flow, tubular type MFCs; (C) flat plate design; (D) single-chamber system; (E) stacked MFC (in which 6 separate MFCs are joined in one reactor block.) (6) 3.4 MATERIALS AND SUBSTRATE: ‘The main four components of an MFC are the anode, cathode, substrate and, if present, the membrane. Anodes: The requirements of an anode material are; highly conductive, non-corrosive, biocompatible, high surface area (area per volume), and if to be scaled up, inexpensive and easily scaled up to larger sizes. The bio film in an MFC asin other bioreactors needs somewhere to grow. The bio film in an MFC grows at the structure surface, hence the need for high surface area which for anodes has reached the highest level of development with the advent of graphite brushes. However of all these properties, the single most important one that is different from other bio film reactors is that the material must be electrically conductive. The simplest and ‘most versatile material for an anode is carbon: relatively inexpensive, easy to handle, has a defined surface area and is available in a wide range of forms such as compact plates, rods, granules, as fibrous material(felt, cloth, paper, fibers, foam), and as glassy carbon, Metal anodes consisting of noncorrosive stainless steel mesh can be utilized, but copper is not usefull due to the toxicity of even trace copper ions to bacteria. Cathodes’ “The design of the cathode is the single greatest challenge for making an MFC a useful and scalable technology. A tri -phase reaction (solid catalyst, ait and water) occurs at air-breathing cathodes as electrodes and is therefore very difficult to engineer. The electrons, protons and oxygen must all meet at the catalyst. Therefore the catalyst must be exposed to both water and air and must have a conductive surface so that the protons and electrons in these different phases can reach the same point. Oxygen is the most obvious choice of electron acceptor for an MFC due to its high oxidation potential, availability, low cost (free), sustainability, and the lack of a chemical ‘waste product (water being the only end product). The choice of the cathode material greatly affects the overall performance of the MFC; as such great care is taken when choosing its ‘material which varies based on whatever its application. The same materials listed for anodes, previously are also used for cathodes. However due to the very slow kinetics of oxygen reduction at a plain carbon material such as a graphite plate, and the resulting large over potential, Pt catalysts are usually used for dissolved oxygen to increase the rate of oxygen reduction . To decrease the costs for the MEC the Pt load can be kept as low as 0.1. mg cm-2(38). The most common commercial cathode material is carbon paper pre-loaded with a Pt catalyst on one side (although it is possible to make yourself in the lab by spraying the Pt onto carbon cloth etc, often resulting, in better performance). The long term stability of Pt requires more study As such there remains a need for new types of inexpensive catalysts such as noble- ‘metal free catalysts that use paralyzed iron (II) phthalate cyanine or Co TMPP (Co- tetra met hoxy phenylporphirine. Membrane: “In a hydrogen fuel cell (HFC), a membrane is an essential component of the system as it separates the two gases (H2 and 02) and provides a ‘method for conducting protons between the two gases. The membrane is therefore referred to as a proton exchange membrane (PEM),”” In MECs however a membrane is not necessarily needed as the protons can be conducted by water. They are only used in MFCs, with the exception of sediment MFCs and single compartment as a means to keep the anode and cathode liquids separate and as a barrier to other species in the cell while allowing protons produced at the anode to migrate to the cathode. Unfortunately MFC membranes are expensive and decrease overall system performance by increasing internal resistance. Substrate: One of the first decisions an MFC researcher will have to make is the choice of Bacterial inoculums and medium. There are ‘many sources from which a researcher could acquire bacteria for the inoculums but one popular choice is wastewater treatment plants because they contain such a rich and diverse supply of bacteria (3). However most researchers will have access to anaerobic mixed consortia from other bioreactors and usually use this as their parent inoculums. Next, is the choice of medium or substrate? In MFCs, substrate is regarded as one of the most important biological factors affecting electricity generation. This is because it serves as a carbon (nutrient) and energy source. The efficiency and economic viability of converting organic ‘wastes to bio energy depend on the characteristics and components of the waste material. (40)The substrate influences integral composition of the bacterial community in the anode bio film and the MBC performance including the power density and Columbic efficiency. Synthetic or chemical wastewater with well-defined composition is used by several researchers as it is easy to control in terms of loading strength, pH and conductivity, If using a synthetic medium the water source must be considered carefully. Por instance chlorine from tap Water would kill the bacteria and hard water may precipitate out required metals. (One advantage of synthetic media is that the researcher can make it as nutrient rich as possible to ensure growth. However, if MCs are to be used in the real world they must be tested for real world substances. One such substance is dairy wastewater whose characteristics contain complex organics, such as polysaccharides, proteins and lipids, which on hydrolysis form sugars, acids and fatty acids, Usually these wastewaters are associated with a high organic load and a high concentration of fermentable substrates with a persistently unpleasant odor. Since dairy based wastewater is rich in biodegradable organics (sugar contributes to 97% of the total COD) and nutrients it is an obvious application for MFCs, There is little research on MFCs used on dairy wastewater however a recent study had some positive findings. The data illustrated that along with good substrate degradation (COD removal, 95.49%). MC also documented good removal of proteins (78.07%), carbohydrates (91.98%) and turbidity (99.02%), a steady increase in MFC performance was observed with increase in substrate load, Maximum volumetric power production (1.10 Wim3; 308 mV; 1.78 mA) was observed at 4.44 kg COD/m3. In view of inherent advantages of the process, if optimized and understood well, MFC treatment of dairy wastewater could be a good replacement for the conventional biological and clectrochemical wastewater treatment processes about 300 million tons of dairy wastewater is generated annually from the Indian dairy industry. Chapter 4 PERFORMANCE AND SCALING UP ‘As mentioned before the main disadvantage of MFCs is their lack of power which is dependent on both biological and electrochemical processes. For instance, substrate conversion rate depends on the amount of bacterial cells, mixing and mass transfer phenomena in the reactor, bacterial kinetics, biomass organic loading rate (gram of substrate per gram of biomass present per day) (44), PEM efficiency and the potential over the load, Over potentials at the electrodes depend on the electrode potential, electrode surface, the electrochemical characteristics of the electrode and the kinetics together with the mechanism of the electron transfer and the current of the MFC. Internal resistance of an MFC is dependent on both the resistance of the electrolyte between the electrodes and membrane resistance (Nafion™ is reputed to have the lowest resistance, For optimal operation, anode and cathode need to be as close together as possible as the greater the distance, the greater the resistance. Proton migration also significantly influences resistance-related losses. ‘The situation at present for MFCs is that they are not economical for scale up. However, the situation is changing, fast. 1, Power densities are continually increasing with air cathodes. High cost anode materials such as graphite plates are being replaced by low cost Materials, better performance materials such as graphite fiber brushes, Precious metal catalysts such as Pt are being replaced with little change in Efficiency with non-precious catalysts using iron or cobalt. Reactor designs are being tested that allow closely spaced electrodes, which as Stated hefore increases power output. Reactors are being designed to maximize electrode packing (surface area per era aween Volume) so that power per reactor volume is increasing. The fact that attention is now shifting from power normalized to electrode surface area, to power per volume reflects a growing appreciation by engineers that this technology is ready to emerge into practical applications. It’s likely that the first cost effective reactor designs will be based on designs utilizing graphite brush electrodes and tubular cathodes. 10 Promising performance in these designs all indicate that MFC based on these brush anodes and tube cathodes are now ready for the next level of testing in larger systems. Through the analysis of performance of these larger systems, it will be possible to evaluate the performance of the system for use as a wastewater treatment technology. MFC. technology’s biggest rival is the, already mature methanogenic anaerobic digestion technology that has seen wide commercial applications. Because it can utilize the same biomass as MFCs in many cases for energy production. MFCs are capable of converting, biomass at temperatures below 20 °C and with low substrate concentrations making MECs the erotically suitable for domestic water treatment with its high volumes and low COD concentrations unlike methanogenic digesters which find operating at such conditions,

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